Method for forming Barrier Layer and the Related Damascene Structure

ABSTRACT

A method for forming barrier layers comprises steps of forming a first metal barrier layer covering a first dielectric layer and contacting a conductive layer through a via of the first dielectric layer, forming a barrier layer of metalized materials on the first metal layer, optionally forming a second metal barrier layer on the barrier layer of metalized materials, removing portions of the barrier layer of metalized materials above the via bottom in the first dielectric layer, and leaving the barrier layer of metalized materials remaining on the via sidewall in the first dielectric layer; and forming a second metal layer covering the barrier layer of metalized materials. The accomplished barrier layers will have lower resistivity on the via bottom in the first dielectric layer and they are capable of preventing copper atoms from diffusing into the dielectric layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent application Ser. No. 11/646,387 filed on Dec. 28, 2006, which is a continuation of U.S. patent application Ser. No. 10/841,562, filed on May 10, 2004, which is a divisional of U.S. patent application Ser. No. 10/461,346, filed Jun. 16, 2003, all of which are commonly assigned.

BACKGROUND

1. Field of the Invention

The present invention relates to a method for the manufacture of semiconductor devices and more particularly to the method for forming a barrier layer in a damascene structure.

2. Description of the Prior Art

In the processes for the manufacture of semiconductor devices, when the active elements of these semiconductor devices are constructed, the following work will be the manufacture of the metal conductive layers above these active elements to complete the electrical interconnection inside the semiconductor devices. The processes for the manufacture of the metal conductive layers are usually as follows: first forming a metal layer above the active regions of the semiconductor devices, second proceeding with photoresist coating, developing, and etching to complete the manufacture of the first metal layer, third depositing a dielectric layer on the first metal layer, and finally proceeding with the manufacture of multiple metal layers dependent on the needs of the different semiconductor devices.

For many years, materials of metal conductive layers of semiconductors are mainly aluminum and aluminum alloys. However, as sizes of semiconductor devices get more and more smaller, operating speeds of semiconductor devices get more and more faster, and power consumptions of semiconductor devices get more and more lower, it is necessary to use metal materials of lower resistivity and dielectric materials of low dielectric constant to complete the electrical interconnection inside semiconductor devices. U.S. Pat. No. 6,489,240 B1 cites using copper and dielectric materials of dielectric constant lower than 4 to complete the electrical interconnection inside semiconductor devices. When copper is used as the material of metal conductors of semiconductors, as shown in FIG. 1A, considering that copper is difficult to be vaporized after etching processes, a dual damascene structure 10 is often used to proceed with copper forming processes inside the dual damascene structure 10. U.S. Pat. No. 6,492,270 B1 mentions the details of forming copper dual damascene. A dual damascene structure 10 comprises a first etch-stop layer 120, a first dielectric layer 160, a second etch-stop layer 140, and a second dielectric layer 180. Before copper processes inside the dual damascene structure 10 above the copper metal layer 100 are performed, as shown in FIG. 1B, a barrier layer 190 has to be formed to prevent copper atoms from diffusing into surrounding dielectric layers.

In order to prevent copper atoms from diffusing into dielectric layers in the prior art, titanium nitride (TiN) or tantalum nitride (TaN) is usually used to form a barrier layer. U.S. Pat. No. 6,541,374 B1 mentions details of forming a barrier layer with TiN. Practically, when the barrier layer 190 is deposited, as a result of the direction of depositing is about perpendicular to the wafer surface, the thickness of the sidewall of the dual damascene structure 10 will be about one-fifth to a half of the thickness above the via bottom in the first dielectric layer 160 and above the trench bottom in the second dielectric layer 180, easily causing that the deposition of the sidewall of the dual damascene structure 10 is incomplete and copper atoms formed later in the dual damascene structure 10 diffuse into surrounding dielectric layers. Consequently the electric property of the surrounding dielectric layers will be affected and then the semiconductor devices will be damaged. Accordingly there is a need for completely depositing a barrier layer of the sidewall of a dual damascene structure 10 to prevent copper atoms from diffusing into surrounding dielectric layers.

In the other hand, the resistivity of nitrided metal materials in the prior art is far more higher than the resistivity of metal materials. Hence if TiN or TaN is used as the material of the barrier layer 190 in the dual damascene structure 10, the resistivity between metals in the dual damascene structure 10 will be so high that the operating speed and the power consumption of the semiconductor devices will be influenced. Therefore there is a need for reducing the resistivity of the barrier layer 190 above the via bottom in the first dielectric layer 160.

BRIEF SUMMARY

One main purpose of the present invention is to use the barrier layer formed by at least two metal layers and a barrier layer of metalized materials to fully prevent copper atoms from diffusing into surrounding dielectric layers.

The other main purpose of the present invention is to reduce the resistivity of the barrier layer above the via bottom in the dielectric layer of a dual damascene structure and to make a good ohmic contact between the barrier layer and the copper layer below the barrier layer and the copper layer later formed above the barrier layer.

From one aspect of the present invention, a method for forming a barrier layer is disclosed. First, a conductive layer is provided. Subsequently, a first dielectric layer is formed on the conductive layer. The first dielectric layer has a via therein. Next, a first barrier metal layer covering the first dielectric layer and the conductive layer is formed. Furthermore, a barrier layer of metalized materials is formed on the first barrier metal layer. Next, portions of the barrier layer of metalized materials above the first barrier metal layer on the via bottom in the first dielectric layer are removed without removing the first barrier metal layer on the via bottom. Portions of the barrier layer of metalized materials remain on the via bottom and the whole via sidewall in the first dielectric layer. Following that, a second barrier metal layer covering the barrier layer of metalized materials is formed. The first barrier metal layer, the barrier layer of metalized materials and the second barrier metal layer are disposed on the via bottom and the whole via sidewall.

From another aspect of the present invention, a method for forming a barrier layer is disclosed. First, a conductive layer is provided. Subsequently, a first dielectric layer is formed on the conductive layer, and the first dielectric layer has a via therein. Next, a first barrier metal layer covering the first dielectric layer and the conductive layer is formed. Furthermore, a barrier layer of metalized materials is formed on the first barrier metal layer. Next, a second barrier metal layer covering the barrier layer of metalized materials is formed. Furthermore, portions of the second barrier metal layer and portions of the barrier layer of metalized materials above the first barrier metal layer on the via bottom in the first dielectric layer are removed. Thus, the second barrier metal layer and the barrier layer of metalized materials remain on the whole via sidewall in the first dielectric layer without removing the first barrier metal layer on the via bottom. Following that, a third barrier metal layer covering the second barrier metal layer is formed. The first barrier metal layer and the third barrier metal layer are disposed on the via bottom. The first barrier metal layer, the barrier layer of metalized materials, the second barrier metal layer and the third barrier metal layer are disposed on the whole via sidewall.

From still another aspect of the present invention, a damascene structure is disclosed. The damascene structure includes a conductive layer, a first dielectric layer, a first barrier metal layer, a barrier layer of metalized materials, a second barrier metal layer and a third barrier metal layer. The first dielectric layer is disposed on the conductive layer, and the first dielectric layer has a via therein. The first barrier metal layer is disposed on the via bottom and the via sidewall in the first dielectric layer. The first barrier metal layer covers the conductive layer on the via bottom. The barrier layer of metalized materials covers the first barrier metal layer on the via sidewall, and exposes the first barrier metal layer on the via bottom. The second barrier metal layer covers the barrier layer of metalized materials on the via sidewall, and exposes the first barrier metal layer on the via bottom. The third barrier metal layer covers the second barrier metal layer on the via sidewall, and covers the first barrier metal layer on the via bottom.

The present invention uses chemical vapor deposition processes or physical vapor deposition processes to form a barrier layer on a conductive layer of a semiconductor device and then uses ion-bombardment to remove metalized materials of higher resistivity to reduce the resistivity of the barrier layer neighboring to the conductive layer.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features and advantages of the various embodiments disclosed herein will be better understood with respect to the following description and drawings, in which like numbers refer to like parts throughout, and in which:

FIG. 1A shows an illustrative chart of a dual damascene structure of the prior art;

FIG. 1B shows an illustrative chart of forming a barrier layer on a dual damascene structure of the prior art;

FIGS. 2A-2E shows an illustrative chart of the steps for forming multi-barrier layers on a dual damascene structure of a first embodiment in the present invention;

FIGS. 3A-3E shows an illustrative chart of the steps for forming multi-barrier layers on a damascene structure of a second embodiment in the present invention;

FIG. 4 shows an illustrative chart of proceeding with physical vapor deposition processes in a plasma reactor in the present invention;

FIG. 5 shows an illustrative chart of proceeding with ion-bombardment processes in a plasma reactor in the present invention;

FIGS. 6D-6E shows an illustrative chart of the steps for forming multi-barrier layers on a dual damascene structure of a third embodiment in the present invention;

FIGS. 7D-7E shows an illustrative chart of the steps for forming multi-barrier layers on a damascene structure of a fourth embodiment in the present invention;

FIGS. 8B-8E shows an illustrative chart of the steps for forming multi-barrier layers on a dual damascene structure of a fifth embodiment in the present invention;

FIGS. 9B-9E shows an illustrative chart of the steps for forming multi-barrier layers on a damascene structure of a sixth embodiment in the present invention;

FIGS. 10E shows an illustrative chart of forming multi-barrier layers on a dual damascene structure of a seventh embodiment in the present invention; and

FIGS. 11E shows an illustrative chart of forming multi-barrier layers on a damascene structure of a eighth embodiment in the present invention.

DETAILED DESCRIPTION

Some embodiments of the invention will be described exquisitely as below. Besides, the invention can also be practiced extensively in other embodiments. That is to say, the scope of the invention should not be restricted by the proposed embodiments. The scope of the invention should be based on the claims proposed later.

In the first preferred embodiment of the present invention, as shown in FIGS. 2A-2E, a dual damascene structure 20 has been already formed on a metal layer 200 of a wafer. The dual damascene structure 20 comprises a first etch-stop layer 220, a first dielectric layer 260 on the first etch-stop layer 220, a second etch-stop layer 240 on the first dielectric layer 260, and a second dielectric layer 280 on the second etch-stop layer 240. Wherein the metal layer 200 is a copper layer. The material of the first etch-stop layer 220 and the second etch-stop layer 240 is the material which can prevent copper atoms from diffusing into surrounding dielectric layers, such as silicon nitride (Si.sub.3N.sub.4). As for the material of the first dielectric layer 260 and the second dielectric layer 280, the material can be silicon dioxide or any other material of which the dielectric constant is lower than 4, such as fluorinated silicate glass (FSG), organo silicate glass, fluorinated amorphous carbon, hydrogenated amorphous carbon, and tetrafluoropoly-p-xylylene. These materials are formed by chemical vapor deposition processes. The material of the first dielectric layer 260 and the second dielectric layer 280 formed can also be hydrogenated silsesquioxane (HSQ), poly arylene ethers (PAE), co-polymar of divinylsiloxane and bis-Benzocyclobutene, aerogel, and xerogel. And these materials are formed by spin coating.

As shown in FIG. 2A, a first tantalum layer 300 is formed on the aforementioned dual damascene structure 20 and the first tantalum layer 300 can be formed by chemical vapor deposition (CVD) processes or physical vapor deposition (PVD) processes. The first tantalum layer 300 is formed by PVD processes in the embodiment. A plasma reactor 60 as shown in FIG. 4, a wafer 62 is secured to a wafer supporter 61 and the wafer supporter 61 is connected to a direct current (DC) bias 65. A tantalum target 64 is secured to a metal target base 63 and the metal target base 63 is grounded. In the PVD processes, argon ions will bombard the tantalum target 64 and the tantalum atoms or ions bombarded out by argon ions will be attracted by the DC bias 65 to deposit on the wafer 62 forming the first tantalum layer 300. In the PVD processes, the process pressure in the plasma reactor 60 is about from 0 torr to 50 milli-torr and the process temperature in the plasma reactor 60 is about from 0 degrees centigrade to 400 degrees centigrade.

As shown in FIG. 2B, a tantalum nitride layer 320 is formed on the first tantalum layer 300 and the tantalum nitride layer 320 can be formed by CVD processes or PVD processes. The tantalum nitride layer 320 is formed by PVD processes in the embodiment. Such as the way of forming the first tantalum layer 300, filling nitrogen gas into the plasma reactor 60 and the nitrogen molecules will react with the tantalum atoms 67 or tantalum ions 66 from the tantalum target 64 which are bombarded by argon ions on the wafer 62 to form the tantalum nitride layer 320. In the PVD processes, the process pressure in the plasma reactor 60 is about from 0 torr to 50 milli-torr and the process temperature in the plasma reactor 60 is about from 0 degrees centigrade to 400 degrees centigrade.

As a result of the resistivity of the tantalum nitride layer 320 varies with the proportion of the nitrogen atoms within the tantalum nitride layer 320, the resistivity is about between 95 micro-ohms centimeter and 14800 micro-ohms centimeter. The resistivity of the tantalum nitride layer 320 is far more than the resistivity of a tantalum layer. The resistivity of the α-phase tantalum layer is about between 15 micro-ohms centimeter and 30 micro-ohms centimeter and the resistivity of the β-phase tantalum layer is about between 150 micro-ohms centimeter and 220 micro-ohms centimeter. However, the resistivity of a copper layer is about 1.7 micro-ohms centimeter. Accordingly in order to reduce the resistivity above the via bottom in the first dielectric layer 260, the tantalum nitride layer 320 above the via bottom in the first dielectric layer 260 has to be removed.

As shown in FIG. 2C, in order to remove the tantalum nitride layer 320 above the via bottom in the first dielectric layer 260, a method of ion-bombardment is taken. As shown in FIG. 5, a plasma reactor 80 is connected by a plasma generating power 84 and a alternating current bias power 83. A wafer 82 is secured to a wafer supporter 81 in the plasma reactor 80. When an ion-bombardment process is proceeded with, a self direct current bias produced by the alternating current bias power 83 attracts argon ions 86 in the plasma 85 to bombard onto the wafer 82. And then tantalum atoms 360 sputtered out from the tantalum nitride layer 320 above the via bottom in the first dielectric layer 260 will deposit on the via sidewall in the first dielectric layer 260. The tantalum nitride layer 320 above the via bottom in the first dielectric layer 260 is removed. Because the marching direction of the argon atoms 86 is perpendicular to the wafer 82 surface, the tantalum nitride layer 320 deposited on the via sidewall in the first dielectric layer 260 sustains less ion-bombardment than the tantalum nitride layer 320 deposited above the via bottom in the first dielectric layer 260 does. In the embodiment, the self direct current bias produced on the wafer supporter 81 is higher than the direct current bias in the PVD processes for deposition of the tantalum layer or the tantalum nitride layer.

After the tantalum nitride layer 320 above the via bottom in the first dielectric layer 260 is removed by the method of ion-bombardment, the structure above the metal layer 200 will be as shown in FIG. 2D. Only the first tantalum layer 300 exists above the via bottom in the first dielectric layer 260. The tantalum atoms 360 sputtered from the via bottom in the first dielectric layer 260 and from the trench bottom in the second dielectric layer 280 will then separately deposit on the sidewall of the downside of the via in the first dielectric layer 260 and on the sidewall of the downside of the trench in the second dielectric layer 280. And then the figure of the structure will be as shown in FIG. 2D. Further as shown in FIG. 2E, a second tantalum layer 340 is formed on the tantalum nitride layer 320 by the method such as the aforementioned method used for forming the first tantalum layer 300. The second tantalum layer 340 can be formed by PVD processes or CVD processes. The second tantalum layer 340 is formed by PVD processes in the embodiment. A plasma reactor 60 as shown in FIG. 4, a wafer 62 is secured to a wafer supporter 61 and the wafer supporter 61 is connected to a direct current (DC) bias 65. A tantalum target 64 is secured to a metal target base 63 and the metal target base 63 is grounded. In the PVD processes, argon ions will bombard the tantalum target 64 and the tantalum atoms or ions bombarded out by argon ions will be attracted by the DC bias 65 to deposit on the wafer 62 forming the second tantalum layer 340. In the PVD processes, the process pressure in the plasma reactor 60 is about from 0 torr to 50 milli-torr and the process temperature in the plasma reactor 60 is about from 0 degrees centigrade to 400 degrees centigrade.

After completing the aforementioned steps, the barrier layers of the dual damascene structure 20 will be as shown in FIG. 2E. Except the tantalum layer composed by the first tantalum layer 300 and the second tantalum layer 340 only exists above the via bottom in the first dielectric layer 260 of the dual damascene structure 20, three barrier layers exist all the other portions of the dual damascene structure 20. These three barrier layers are the first tantalum layer 300, the tantalum nitride layer 320, and the second tantalum layer 340 respectively. The tantalum is used because it has good adhesion to copper. The tantalum nitride is capable of preventing copper atoms from diffusing into surrounding dielectric layers. The barrier structure of the three barrier layers is thicker than the barrier layer of the side wall portion of a dual damascene structure in the prior art to prevent copper atoms from diffusing into surrounding dielectric layers. Besides, the tantalum layer has 30% lower resistivity above the via bottom of the first dielectric layer than the resistivity in the prior art. Further the tantalum layer will have good ohmic contact with the copper layer below and the copper layer formed inside the dual damascene structure later.

In the other preferred embodiment of the present invention, as shown in FIGS. 3A-3E, a damascene structure 40 has been already formed on a metal layer 400 of a wafer. The damascene structure 40 comprises an etch-stop layer 420 and a dielectric layer 440 on the etch-stop layer 420. Wherein the metal layer 400 is a copper layer. The material of the etch-stop layer 420 is the material which can prevent copper atoms from diffusing into surrounding dielectric layers, such as silicon nitride (Si.sub.3N.sub.4). As for the material of the dielectric layer 440, the material can be silicon dioxide or any other material of which the dielectric constant is lower than 4, such as fluorinated silicate glass (FSG), organo silicate glass, fluorinated amorphous carbon, hydrogenated amorphous carbon, and tetrafluoropoly-p-xylylene. These materials are formed by chemical vapor deposition processes. The material of the dielectric layer 440 can also be hydrogenated silsesquioxane (HSQ), poly arylene ethers (PAE), co-polymar of divinylsiloxane and bis-Benzocyclobutene, aerogel, and xerogel. And these materials are formed by spin coating.

As shown in FIG. 3A, a first tantalum layer 460 is formed on the aforementioned damascene structure 40 and the first tantalum layer 460 can be formed by chemical vapor deposition (CVD) processes or physical vapor deposition (PVD) processes. The first tantalum layer 460 is formed by PVD processes in the embodiment. A plasma reactor 60 as shown in FIG. 4, a wafer 62 is secured to a wafer supporter 61 and the wafer supporter 61 is connected to a direct current (DC) bias 65. A tantalum target 64 is secured to a metal target base 63 and the metal target base 63 is grounded. In the PVD processes, argon ions will bombard the tantalum target 64 and the tantalum atoms or ions bombarded out by argon ions will be attracted by the DC bias 65 to deposit on the wafer 62 forming the first tantalum layer 460. In the PVD processes, the process pressure in the plasma reactor 60 is about from 0 torr to 50 milli-torr and the process temperature in the plasma reactor 60 is about from 0 degrees centigrade to 400 degrees centigrade.

As shown in FIG. 3B, a tantalum nitride layer 480 is formed on the first tantalum layer 460 and the tantalum nitride layer 480 can be formed by CVD processes or PVD processes. The tantalum nitride layer 480 is formed by PVD processes in the embodiment. Such as the way of forming the first tantalum layer 460, filling nitrogen gas into the plasma reactor 60 and the nitrogen molecules will react with the tantalum atoms 67 or tantalum ions 66 from the tantalum target 64 which are bombarded by argon ions on the wafer 62 to form the tantalum nitride layer 480. In the PVD processes, the process pressure in the plasma reactor 60 is about from 0 torr to 50 milli-torr and the process temperature in the plasma reactor 60 is about from 0 degrees centigrade to 400 degrees centigrade.

As a result of the resistivity of the tantalum nitride layer 480 varies with the proportion of the nitrogen atoms within the tantalum nitride layer 480, the resistivity is about between 95 micro-ohms centimeter and 14800 micro-ohms centimeter. The resistivity of the tantalum nitride layer 480 is far more than the resistivity of a tantalum layer. The resistivity of the α-phase tantalum layer is about between 15 micro-ohms centimeter and 30 micro-ohms centimeter and the resistivity of the β-phase tantalum layer is about between 150 micro-ohms centimeter and 220 micro-ohms centimeter. However, the resistivity of a copper layer is about 1.7 micro-ohms centimeter. Accordingly in order to reduce the resistivity above the via bottom in the dielectric layer 440, the tantalum nitride layer 480 above the via bottom in the dielectric layer 440 has to be removed.

As shown in FIG. 3C, in order to remove the tantalum nitride layer 480 above the via bottom in the dielectric layer 440, a method of ion-bombardment is taken. As shown in FIG. 5, a plasma reactor 80 is connected by a plasma generating power 84 and a alternating current bias power 83. A wafer 82 is secured to a wafer supporter 81 in the plasma reactor 80. When an ion-bombardment process is proceeded with, a self direct current bias produced by the alternating current bias power 83 attracts argon ions 86 in the plasma 85 to bombard onto the wafer 82. And then tantalum atoms 520 sputtered out from the tantalum nitride layer 480 above the via bottom in the dielectric layer 440 will deposit on the via sidewall in the dielectric layer 440. The tantalum nitride layer 480 above the via bottom in the dielectric layer 440 is removed. Because the marching direction of the argon atoms 86 is perpendicular to the wafer 82 surface, the tantalum nitride layer 480 deposited on the via sidewall in the dielectric layer 440 sustains less ion-bombardment than the tantalum nitride layer 480 deposited above the via bottom in the dielectric layer 440 does. In the embodiment, the self direct current bias produced on the wafer supporter 81 is higher than the direct current bias in the PVD processes for deposition of the tantalum layer or the tantalum nitride layer.

After the tantalum nitride layer 480 above the via bottom in the dielectric layer 440 is removed by the method of ion-bombardment, the structure above the metal layer 400 will be as shown in FIG. 3D. Only the first tantalum layer 460 exists above the via bottom in the dielectric layer 440. The tantalum atoms 520 sputtered from the via bottom in the dielectric layer 440 will then deposit on the sidewall of the downside of the via in the dielectric layer 440. And then the figure of the structure will be as shown in FIG. 3D. Further as shown in FIG. 3E, a second tantalum layer 500 is formed on the tantalum nitride layer 480 by the method such as the aforementioned method used for forming the first tantalum layer 460. The second tantalum layer 500 can be formed by PVD processes or CVD processes. The second tantalum layer 500 is formed by PVD processes in the embodiment. A plasma reactor 60 as shown in FIG. 4, a wafer 62 is secured to a wafer supporter 61 and the wafer supporter 61 is connected to a direct current (DC) bias 65. A tantalum target 64 is secured to a metal target base 63 and the metal target base 63 is grounded. In the PVD processes, argon ions will bombard the tantalum target 64 and the tantalum atoms or ions bombarded out by argon ions will be attracted by the DC bias 65 to deposit on the wafer 62 forming the second tantalum layer 500. In the PVD processes, the process pressure in the plasma reactor 60 is about from 0 torr to 50 milli-torr and the process temperature in the plasma reactor 60 is about from 0 degrees centigrade to 400 degrees centigrade.

After completing the aforementioned steps, the barrier layers of the damascene structure 40 will be as shown in FIG. 3E. Except the tantalum layer composed by the first tantalum layer 460 and the second tantalum layer 500 only exists above the via bottom in the dielectric layer 440 of the damascene structure 40, three barrier layers exist all the other portions of the damascene structure 40. These three barrier layers are the first tantalum layer 440, the tantalum nitride layer 480, and the second tantalum layer 500 respectively. The tantalum is used because it has good adhesion to copper. The tantalum nitride is capable of preventing copper atoms from diffusing into surrounding dielectric layers. The barrier structure of the three barrier layers is thicker than the barrier layer of the side wall portion of a dual damascene structure in the prior art to prevent copper atoms from diffusing into surrounding dielectric layers. Besides, the tantalum layer has 30% lower resistivity above the via bottom of the dielectric layer than the resistivity in the prior art. Further the tantalum layer will have good ohmic contact with the copper layer below and the copper layer formed inside the damascene structure later.

It is noted that the barrier layer of metalized materials disposed on the via bottom may be punched through in the above-mentioned embodiments, and may just be thinned in other embodiments. Please refer to FIGS. 6D-6E, which illustrate a method for forming multi-barrier layers on a dual damascene structure of a third embodiment in the present invention. In order to compare to the first embodiment discussed previously, same labels will be carried forward through FIGS. 6D-6E.

As shown in FIG. 6D, a dual damascene structure 70 is formed on a metal layer 200 of a wafer, a first tantalum layer 300 is formed on the dual damascene structure 70, a tantalum nitride layer 320 a is formed on the first tantalum layer 300, and an ion-bombardment process may be performed on the tantalum nitride layer 320 a through the steps shown in FIG. 2A-2C. One difference between the first embodiment and the third embodiment is that the ion-bombardment process does not punch through the tantalum nitride layer 320 a disposed on the via bottom in the third embodiment. In other words, only portions of the tantalum nitride layer 320 a on the via bottom in the first dielectric layer 260 are removed. Portions of the tantalum nitride layer 320 a may still remain on the via bottom and the via sidewall in the first dielectric layer 260 without removing the first tantalum layer 300 on the via bottom. In the ion-bombardment process, a self direct current bias attracts argon ions 86 to bombard onto the tantalum nitride layer 320 a, and the tantalum atoms 360 sputtered out from the tantalum nitride layer 320 on the via bottom toward the via sidewall. Therefore, the tantalum nitride layer 320 a may still remain on the whole via bottom in the first dielectric layer 260, and portions of the tantalum nitride layer 320 a disposed on the via bottom is thinned by the ion-bombardment process.

As shown in FIG. 6E, a second tantalum layer 340 is formed on the tantalum nitride layer 320 a. After completing the aforementioned steps, the tri-layer barrier structure including the first tantalum layer 300, the tantalum nitride layer 320 a and the second tantalum layer 340 may be disposed on both the via bottom and the whole via sidewall. Portions of the tantalum nitride layer 320 a disposed on the via bottom may be thinner than portions of the tantalum nitride layer 320 a disposed on the via sidewall. After the second tantalum layer 340 is formed, a conductive layer, such as copper layer, (not shown) may be formed on the second tantalum layer 340 and filling the dual damascene structure 70. Since the resistivity of the tantalum nitride layer 320 a varies with the proportion of the nitrogen atoms within the tantalum nitride layer 320 a, and the tantalum nitride layer 320 a may be thinned, the resistivity above the via bottom in the first dielectric layer 260 can also be effectively reduced.

The ion-bombardment process without punching through the tantalum nitride layer may also be applied to a damascene structure. Please refer to FIGS. 7D-7E, which illustrate a method for forming multi-barrier layers on a damascene structure of a fourth embodiment in the present invention. In order to compare to the second embodiment discussed previously, same labels will be carried forward through FIGS. 7D-7E.

As shown in FIG. 7D, a damascene structure 90 is formed on a metal layer 400 of a wafer, a first tantalum layer 460 is formed on the dual damascene structure 90, a tantalum nitride layer 480 a is formed on the first tantalum layer 460, and an ion-bombardment process may be performed on the tantalum nitride layer 480 a through the steps shown in FIG. 3A-3C. One difference between the second embodiment and the fourth embodiment is that the ion-bombardment process does not punch through the tantalum nitride layer 480 a disposed on the via bottom in the fourth embodiment. In other words, only portions of the tantalum nitride layer 480 a on the via bottom in the dielectric layer 440 are removed. Portions of the tantalum nitride layer 480 a may still remain on the whole bottom and the whole via sidewall in the dielectric layer 440 without removing the first tantalum layer 460 on the via bottom.

As shown in FIG. 7E, a second tantalum layer 500 is formed on the tantalum nitride layer 480 a. After completing the aforementioned steps, the tri-layer barrier structure including the first tantalum layer 300, the tantalum nitride layer 480 a and the second tantalum layer 500 may be disposed on both the via bottom and the whole via sidewall. Portions of the tantalum nitride layer 480 a disposed on the via bottom may be thinner than portions of the tantalum nitride layer 480 a disposed on the via sidewall. Since the resistivity of the tantalum nitride layer 480 a varies with the proportion of the nitrogen atoms within the tantalum nitride layer 480 a, and the tantalum nitride layer 480 a may be thinned, the resistivity above the via bottom in the dielectric layer 440 can also be effectively reduced.

Moreover, the multi-barrier layers formed on the damascene structure or on the dual damascene structure may include more than three barrier layers in other embodiments. Please refer to FIGS. 8B-8E, which illustrate a method for forming multi-barrier layers on a dual damascene structure of a fifth embodiment in the present invention. In order to compare to the first embodiment discussed previously, same labels will be carried forward through FIGS. 8B-8E.

As shown in FIG. 8B, a dual damascene structure 30 is first formed on a metal layer 200 of a wafer, a first tantalum layer 300 is formed on the damascene structure 50, and a tantalum nitride layer 320 is formed on the first tantalum layer 300 through the steps shown in FIG. 2A-2B. One difference between the first embodiment and the fifth embodiment is that a second tantalum layer 340 is further formed on the tantalum nitride layer 320 before the ion-bombardment process in the fifth embodiment.

As shown in FIG. 8C-8D, an ion-bombardment process may be next performed on both the second tantalum layer 340 and the tantalum nitride layer 320. The ion-bombardment process may first remove the second tantalum layer 340, and may subsequently remove the tantalum nitride layer 320 after the second tantalum layer 340 is punched through. In this embodiment, the ion-bombardment process may punch through both the second tantalum layer 340 and the tantalum nitride layer 320 disposed on the via bottom. Only the first tantalum layer 300 exists above the via bottom in the first dielectric layer 260. The ion-bombardment process may leave the second tantalum layer 340 and the tantalum nitride layer 320 remaining on the whole via sidewall in the first dielectric layer 260 without removing the first tantalum layer 300 on the via bottom.

As shown in FIG. 8E, a third tantalum layer 350 is formed on the second tantalum layer 340 and the tantalum nitride layer 320. After completing the aforementioned steps, both the first tantalum layer 300 and the third tantalum layer 350 may be disposed on the via bottom; and the first tantalum layer 300, the tantalum nitride layer 320, the second tantalum layer 340 and the third tantalum layer 350 may be disposed on the whole via sidewall. In other words, there are four barrier layers, which include the first tantalum layer 300, the tantalum nitride layer 320, the second tantalum layer 340 and the third tantalum layer 350, on the via sidewall to prevent copper atoms from diffusing into surrounding dielectric layers. Portions of the tantalum nitride layer 320 disposed on the via bottom is punched through or thinned. After the third tantalum layer 350 is formed, a conductive layer, such as copper layer, (not shown) may be formed on the third tantalum layer 350 and filling the dual damascene structure 30. Since the resistivity of the tantalum nitride layer 320 varies with the proportion of the nitrogen atoms within the tantalum nitride layer 320, and the tantalum nitride layer 320 may be punched through or thinned, the resistivity above the via bottom in the first dielectric layer 260 can also be effectively reduced.

It can be understood that portions of the tantalum nitride layer 320 and/or portions of the second tantalum layer 340 may still remain on the via bottom in other embodiments, as shown in FIG. 10E.

The four-barrier layers may also be applied to a damascene structure. Please refer to FIGS. 9B-9E, which illustrate a method for forming multi-barrier layers on a damascene structure of a sixth embodiment in the present invention. In order to compare to the second embodiment discussed previously, same labels will be carried forward through FIGS. 9B-9E.

As shown in FIG. 9B, a damascene structure 50 is first formed on a metal layer 400 of a wafer, a first tantalum layer 460 is formed on the damascene structure 50, and a tantalum nitride layer 480 is formed on the first tantalum layer 460 through the steps shown in FIG. 3A-3B. One difference between the second embodiment and the sixth embodiment is that a second tantalum layer 500 is further formed on the tantalum nitride layer 480 before the ion-bombardment process in the sixth embodiment.

As shown in FIG. 9C-9D, an ion-bombardment process may be performed on both the second tantalum layer 500 and the tantalum nitride layer 480 on the via bottom. The ion-bombardment process may first remove the second tantalum layer 500, and may subsequently remove the tantalum nitride layer 480. In this embodiment, the ion-bombardment process may punch through both the second tantalum layer 500 and the tantalum nitride layer 480 disposed on the via bottom. The ion-bombardment process may leave both the second tantalum layer 500 and the tantalum nitride layer 480 remaining on the whole via sidewall in the dielectric layer 440 without removing the first tantalum layer 460 on the via bottom.

As shown in FIG. 9E, a third tantalum layer 510 is formed on the second tantalum layer 500 and the tantalum nitride layer 480. After completing the aforementioned steps, the first tantalum layer 460 and the third tantalum layer 510 may be disposed on the via bottom; and the first tantalum layer 460, the tantalum nitride layer 480, the second tantalum layer 500 and the third tantalum layer 510 may be disposed on the whole via sidewall. In other words, there are four barrier layers, which include the first tantalum layer 460, the tantalum nitride layer 480, the second tantalum layer 500 and the third tantalum layer 510, on the via sidewall to prevent copper atoms from diffusing into surrounding dielectric layers. Portions of the tantalum nitride layer 480 disposed on the via bottom is punched through or thinned. Since the resistivity of the tantalum nitride layer 480 varies with the proportion of the nitrogen atoms within the tantalum nitride layer 480, and the tantalum nitride layer 480 may be punched through or thinned, the resistivity above the via bottom in the dielectric layer 440 can also be effectively reduced.

It can be understood that portions of the second tantalum layer 500 and portions of the tantalum nitride layer 480 may still remain on the via bottom in other embodiments, as shown in FIG. 11E.

The above description is given by way of example, and not limitation. Given the above disclosure, one skilled in the art could devise variations that are within the scope and spirit of the invention disclosed herein, including configurations ways of the recessed portions and materials and/or designs of the attaching structures. Further, the various features of the embodiments disclosed herein can be used alone, or in varying combinations with each other and are not intended to be limited to the specific combination described herein. Thus, the scope of the claims is not to be limited by the illustrated embodiments. As with the operating sequence of the present invention, many variations are possible, and any rearrangement of the operating sequence for achieving same functionality is still within the spirit and scope of the invention. 

1. A method for forming a barrier layer, comprising: providing a conductive layer; forming a first dielectric layer on the conductive layer, the first dielectric layer having a via therein; forming a first barrier metal layer covering the first dielectric layer and the conductive layer; forming a barrier layer of metalized materials on the first barrier metal layer; removing portions of the barrier layer of metalized materials on the via bottom; and forming a second barrier metal layer covering the barrier layer of metalized materials.
 2. The method for forming a barrier layer according to claim 1, wherein the step of removing portions of the barrier layer of metalized materials comprises leaving portions of the barrier layer of metalized materials on the via bottom and the barrier layer of metalized materials on the via sidewall.
 3. The method for forming a barrier layer according to claim 1, wherein the first barrier metal layer, the barrier layer of metalized materials and the second barrier metal layer are disposed on the via bottom and the whole via sidewall after the second barrier metal layer is formed.
 4. The method for forming a barrier layer according to claim 1, wherein the barrier layer of metalized materials on the via bottom in the first dielectric layer is removed by an ion-bombardment process.
 5. The method for forming a barrier layer according to claim 4, wherein metal atoms are bombarded out from the barrier layer of metalized materials toward the via sidewall.
 6. The method for forming a barrier layer according to claim 4, wherein the ion-bombardment process employs argon ions.
 7. The method for forming a barrier layer according to claim 1, further comprising forming a second dielectric layer on the first dielectric layer before forming the first barrier metal layer wherein a trench is in the second dielectric layer and the trench in the second dielectric layer is connected to the via in the first dielectric layer.
 8. The method for forming a barrier layer according to claim 1, wherein the first and the second barrier metal layers are tantalum layers, the barrier layer of metalized materials is a tantalum nitride layer, and the conductive layer is a copper layer.
 9. The method for forming a barrier layer according to claim 1, wherein the portions of the barrier layer of metalized materials disposed on the via bottom are thinner than the portions of the barrier layer of metalized materials disposed on the via sidewall.
 10. A method for forming a barrier layer, comprising; providing a conductive layer; forming a first dielectric layer on the conductive layer, the first dielectric layer having a via therein; forming a first barrier metal layer covering the first dielectric layer and the conductive layer; forming a barrier layer of metalized materials on the first barrier metal layer; forming a second barrier metal layer covering the barrier layer of metalized materials; removing the second barrier metal layer and at least portions of the barrier layer of metalized materials on the via bottom; and forming a third barrier metal layer covering the second barrier metal layer.
 11. The method for forming a barrier layer according to claim 10, wherein the step of removing the second barrier metal layer and the portions of the barrier layer of metalized materials comprises leaving the second barrier metal layer and the barrier layer of metalized materials remaining on the whole via sidewall.
 12. The method for forming a barrier layer according to claim 10, wherein the first barrier metal layer and the third barrier metal layer are disposed on the via bottom, and the first barrier metal layer, the barrier layer of metalized materials, the second barrier metal layer and the third barrier metal layer are disposed on the whole via sidewall.
 13. The method for forming a barrier layer according to claim 10, wherein the step of removing the second barrier metal layer and the portions of the barrier layer of metalized materials comprises leaving portions of the barrier layer of metalized materials on the via bottom and the second barrier metal layer and the barrier layer of metalized materials remaining on the whole via sidewall.
 14. The method for forming a barrier layer according to claim 10, wherein the first barrier metal layer, the barrier layer of metalized materials and the third barrier metal layer are disposed on the via bottom, and the first barrier metal layer, the barrier layer of metalized materials, the second barrier metal layer and the third barrier metal layer are disposed on the whole via sidewall.
 15. The method for forming a barrier layer according to claim 10, wherein the second barrier metal layer and the barrier layer of metalized materials on the via bottom in the first dielectric layer is removed by an ion-bombardment process.
 16. The method for forming a barrier layer according to claim 15, wherein metal atoms are bombarded out from the barrier layer of metalized materials toward the via sidewall.
 17. The method for forming a barrier layer according to claim 15, wherein the ion-bombardment process employs argon ions.
 18. The method for forming a barrier layer according to claim 10, further comprising forming a second dielectric layer on the first dielectric layer before forming the first barrier metal layer wherein a trench is in the second dielectric layer and the trench in the second dielectric layer is connected to the via in the first dielectric layer.
 19. A damascene structure, comprising: a conductive layer; a first dielectric layer disposed on the conductive layer, the first dielectric layer having a via therein; a first barrier metal layer disposed on the via bottom and the via sidewall in the first dielectric layer, the first barrier metal layer covering the conductive layer on the via bottom; a barrier layer of metalized materials covering the first barrier metal layer on the via sidewall, exposing the first barrier metal layer on the via bottom; a second barrier metal layer covering the barrier layer of metalized materials on the via sidewall, exposing the first barrier metal layer on the via bottom; and a third barrier metal layer covering the second barrier metal layer on the via sidewall, and covering the first barrier metal layer on the via bottom.
 20. The damascene structure according to claim 19, wherein the first and the second barrier metal layers are tantalum layers, the barrier layer of metalized materials is a tantalum nitride layer, and the conductive layer is a copper layer. 